Sodium bicarbonate (NaHCO3) is a mild alkaline compound with a wide range of applications including uses in human food, animal feed, flue gas treatment, and chemical industries. World production of sodium bicarbonate in 2008 is estimated at 2.8 million tons. Most of its production derives from natural and synthetic sodium carbonate (Na2CO3). The production of sodium bicarbonate is mainly made by the carbonation of a sodium carbonate aqueous solution with gaseous CO2. The sodium carbonate aqueous solution may come from purified sodium carbonate dissolved in water, or a from a partially decarbonated slurry of crude sodium bicarbonate from the Solvay process, or from a sodium carbonate solution taken out from a sodium carbonate crystallization unit fed with solutions deriving from trona or nahcolite ores.
When sodium bicarbonate is made from solid refined sodium carbonate, the content of sodium carbonate in impurities, such as alkaline metal water-soluble salts, is low enough so that those impurities may efficiently be extracted from the sodium bicarbonate process with the final produced sodium bicarbonate. Therefore no specific purge of such impurities is needed in the corresponding sodium bicarbonate process.
Yet when sodium bicarbonate is made from sodium carbonate streams from either synthetic soda ash (Solvay or derived Hou processes) or from natural minerals (trona or nahcolite related processes), those sodium carbonate streams contain higher levels of soluble impurities, and a purge is needed to control the level of impurities in the sodium bicarbonate process. This purge is generally high and fed back in the corresponding sodium carbonate process or sent to high volumes deposit ponds such as the processes described in U.S. Pat. No. 7,507,388 or in US2009/0291038 or in US2011/112298.
Aside sodium bicarbonate, sodium carbonate, also called soda ash, is a large volume alkali commodity with a total production in 2008 of 48 million tons worldwide, which finds major use in the glass, chemicals, detergents industries, and also in the sodium bicarbonate production industry. The main processes for sodium carbonate production are the Solvay ammonia synthetic process, the ammonium chloride process (Hou process) derived from the Solvay process, and the trona-based processes.
Trona ore is a mineral that contains up to 99% sodium sesquicarbonate (Na2CO3.NaHCO3.2H2O). The sodium sesquicarbonate found in trona ore is a complex salt that is soluble in water and dissolves to yield approximately 5 parts by weight sodium carbonate (Na2CO3) and 4 parts sodium bicarbonate (NaHCO3). The trona ore is processed to remove the insoluble material, the organic matter and other impurities to recover the valuable alkali contained in the trona.
Trona-based soda ash is obtained from trona ore deposits in Green River (Wyoming), Turkey, China, and Kenya either by conventional underground mining techniques, by solution mining or lake waters processing. The trona-based sodium carbonate from Wyoming comprises about 90% of the total U.S. soda ash production. Sodium carbonate finds major use in the glass-making industry and for the production of baking soda, detergents and paper products.
A typical analysis of the trona ore in Green River is as follows:
TABLE 1ConstituentWeight PercentNa2CO343.6NaHCO334.5H2O (crystalline and free moisture)15.4NaCl0.01Na2SO40.01Fe2O30.14Insolubles6.3Organics0.3
Trona deposits contain diverse highly soluble impurities such as alkaline metal halides (sodium chloride, potassium chloride, sodium fluoride, . . . ), alkaline metal sulfates (sodium sulfate, potassium sulfate, . . . ), alkaline metal nitrate (sodium nitrate, potassium nitrate, . . . ), alkaline metal borate, alkaline metal phosphates, etc. . . . . Those highly soluble impurities are in various proportions depending on the geographic location of the deposits. In particular, sodium chloride and sodium sulfate may represent several percent or several ten percent of trona ore depending on the geographic location.
Trona deposits also include slightly soluble mineral or organic impurities. Examples of slightly soluble mineral are: alkali metal and alkali earth metal silicates, aluminates, titanates, vanadates, metallic compounds and salts.
The organic impurities come from organic sediments that were captured during the formation of the deposits and that frequently have formed oil shales during geological aging. Both mineral and organic soluble impurities may also be partially generated during the trona processing in the mine or on surface operations. In particular thermal treatments, such as calcination, generally amplify the quantity of some soluble impurities such as sodium silicates, and sodium salts of organic compounds by thermal saponification.
Other “insoluble” or very slightly water-soluble mineral impurities found in trona or adjacent to trona deposits are generally mixtures of different minerals, the most frequent of which are calcite, dolomite, pirssonite, zeolite, feldspar, clay minerals, iron/aluminum silicates, and calcium sulfate.
Two main techniques well known in the art are used to recover trona ore from trona ore deposits. The first technique is a mechanical mining, also called conventional mining, such as a room and pillar panel operation or a longwall operation. The second technique is a solution mining recovering wherein trona is dissolved with water and recovered as a solution.
Among the several ways in which sodium carbonate can be recovered from trona ore that contains other salts and impurities, the most widely practiced is the so called “monohydrate process”.
In that process a mined trona ore is crushed, then calcined into crude sodium carbonate, then leached with water, the resulting water solution is purified and fed to a crystallization unit where pure sodium carbonate monohydrate crystals are crystallized. The monohydrate crystals are separated from the mother liquor and then dried into anhydrous sodium carbonate. Most of the mother liquor is recycled into the crystallization unit. However, the soluble impurities contained in the trona ore, tend to accumulate into the crystallization unit. To avoid buildup of impurities, the mother liquor must be purged, and a purge stream must exit the sodium carbonate crystallization unit. The sodium carbonate purge stream, which represents important quantities for industrial monohydrate plants, is commonly sent to an evaporative pond, also called tailings pond. The significant quantity of alkali which is contained in the sodium carbonate purge stream is consequently lost. Moreover, the stocking of large quantities of sodium carbonate purge streams in evaporative ponds raise environmental problems, because of the scarce availability of new areas for stocking.
On the other side, sodium bicarbonate is a product with a wide range of interesting properties and a very wide range of applications from high tech ingredients for the pharma industry to the human food and animal feed, and to the use in flue gas treatment. In flue gas treatment, sodium bicarbonate is most likely among the most efficient chemicals for the removal of a wide range of pollutants (most notably the acidic ones such as HCl and sulfur oxides). Its use is limited only by the competition of less efficient but much cheaper chemicals such as lime or even limestone.
The production of sodium bicarbonate is currently almost entirely made by the carbonation of sodium carbonate. In Europe, the carbonation is usually performed in situ in the soda ash plants from CO2 coproduced during the production of soda ash (mainly the CO2 generation in the lime kilns). In the United States, the carbonation is usually made in separate plants which purchase independently the soda ash and the CO2 and combine them.
An alternative method for making sodium bicarbonate is by cooling crystallization of a liquor containing sodium bicarbonate. For example, U.S. Pat. No. 6,699,447 describes a sodium bicarbonate production from nahcolite. The method for producing sodium bicarbonate from a nahcolite deposit comprises injecting water or other aqueous solution at a temperature of at least 250° F. into the deposit, dissolving sodium bicarbonate in the hot water to form a production solution and subjecting the production solution to multiple stages of cooling crystallization. The sodium bicarbonate crystals may be dewatered and dried to form a commercial sodium bicarbonate product.
Because of the nature of the bicarbonate production process, the price for sodium bicarbonate is higher than the price of soda ash. With such economics, the uses of sodium bicarbonate will generally be limited by the competition of cheaper substitutes, most notably in flue gas treatment methods.
US2003/0017099 discloses a process for the joint production of sodium carbonate and bicarbonate, according to which solid trona is dissolved in water and the resulting water solution is fed into a monohydrate crystallization unit in order to produce sodium carbonate. The monohydrate purge is introduced into a decahydrate crystallization unit and the decahydrate crystals converted into sodium bicarbonate. It has been observed that this process is not efficient when the monohydrate purge, depending on the trona source, contains high levels of impurities. In particular, the sodium chloride content of the trona ore can vary depending on the precise trona vein which is exploited. High levels of sodium chloride in the monohydrate purge prevent smooth crystallization of decahydrate.
Several technical alternatives have been proposed to reduce the purge volume from soda ash plants.
US2003/0143149 discloses a process for recovering sodium-based chemicals from sodium carbonate streams such as recycle, purge, and waste streams from sodium carbonate crystallization units, mine water, evaporative pond water and sodium carbonate decahydrate deposits. The sodium bicarbonate from those streams is partially destroyed by a decarbonization and the resulting stream is fed mainly back to a sodium carbonate monohydrate crystallization unit, and the remainder of the resulting decarbonized stream is fed to a sodium carbonate decahydrate crystallization unit, from which purified decahydrate is recovered and recycled to monohydrate crystallization unit and a purge concentrated in impurity such as sodium sulfate is disposed of. Although the purge reduction factor of this process is limited, because, when high concentration of impurities is reached, sodium carbonate and sodium sulfate form decahydrated mixed salts. And if high amounts of sodium sulfate are recycled back to carbonate monohydrate crystallization unit, they generate burkeite crystals (Na2CO3.2Na2SO4) that are detrimental to sodium carbonate monohydrate quality.
US2004/0057892 discloses a process for the production of sodium carbonate and bicarbonate, according to a monohydrate purge from a monohydrate sodium carbonate crystallization unit is introduced into a sodium carbonate decahydrate crystallization unit and the purified decahydrate crystals are converted into sodium bicarbonate. It has been observed that this process is not efficient when the monohydrate purge, depending on the trona source, contains high levels of impurities. High levels of sodium chloride in the monohydrate purge prevent smooth crystallization of sodium carbonate decahydrate.
U.S. Pat. No. 7,507,388 discloses a process for the production of sodium carbonate and bicarbonate, from a pre-purified solution comprising bicarbonate which is first partially decarbonized and then used in both a sodium bicarbonate line and a sodium carbonate monohydrate line. The purge stream of the sodium carbonate monohydrate crystallization unit is either sent into a mixed sodium carbonate decahydrate and sodium sesquicarbonate line wherein resulting filtrate is discarded as the final purge of the process or sent after dilution into a light soda ash line comprising an intermediate sodium bicarbonate carbonation step, the bicarbonate is separated from the filtrate, and this filtrate is also disposed as a final purge. The taught total amounts of generated purges is very high (1.28 tons of purges per ton of dense soda ash) and corresponds to 6 to 15 weight percent of purged sodium carbonate per ton of produced dense soda ash.
US2009/0291038 (Solvay) discloses a process for the joint production of sodium carbonate and sodium bicarbonate crystals, according to which a solid powder derived from sodium sesquicarbonate such as calcined trona is dissolved in water, the resulting water solution is introduced into a crystallization unit, wherein sodium carbonate crystals and a mother liquor are produced, part of the mother liquor is taken out of the crystallization unit (purge of the sodium carbonate crystallization unit) and is carbonized (carbonated) to produce valuable sodium bicarbonate crystals and a second mother liquor, the second mother liquor is optionally decarbonized (debicarbonated) and then sent to a storage pond. In this document, it is taught that the mother liquor used for sodium bicarbonate crystallization should contain preferably at least 175 g/kg of sodium carbonate and not more than 60 g/kg of sodium chloride, and not more than 20 g/kg of sodium sulfate. Consequently, the purge level of sodium alkali (carbonate or bicarbonate) sent to a pond is reduced compared to a decahydrate treatment of the purge but is still important and represents important volumes sent into ponds.
US2011/112298 discloses a method for extending the life of tailings ponds produced from purge streams containing sodium carbonate wherein the purge stream is treated with gaseous carbon dioxide, similar to the US2009/0291038 process, to produce sodium bicarbonate or sodium sesquicarbonate before being introduced in the pond. The produced sodium bicarbonate may be recovered before the introduction of the treated purge stream into tailings pond or recovered after its deposition into the pond. The document is silent on further valorizing the obtained aqueous purge when sodium bicarbonate is recovered.
However, there is still a need in the sodium carbonate and bicarbonate industry, taking into account sustainable development, to be able to further reduce the purge volume which is sent to tailings ponds and reducing the loss of alkali, without impairing operation conditions.